JPS61151143A - Manufacture of alkoxyhalide - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION [Summary of the Invention] Discloses a method for producing alkyl alkoxy, arylalkoxy or alkylaryl alkoxy halides, wherein these halides are prepared from alcohols, phenols, or alkylphenols according to the first table of the periodic table.
Reaction with ethylene oxide and/or propylene oxide in the presence of a Group A or Group IIA soluble metal or metal compound to form an alkoxy alcohol, which is then directly reacted with a halogenating agent in the continuous presence of a catalyst. Manufactured by

Thus, costs are reduced and product yields are increased.

[Industrial application field]

The present invention relates to a process for producing alkylalkoxy, arylalkoxy or alkylaryl alkoxy halides suitable for use as intermediates in the production of surfactants.

[Conventional technology]

Many attempts have been made to develop surfactant compositions for use in improving oil recovery, and patent publications are extremely replete with descriptions of compositions [eg, U.S. Pat. No. 4,424.
No. 135, No. 4, No. 159.037, No. 4,110,
No. 228, No. 4,066.124 and No. 4.01
8.See No. 278].

An overview of useful techniques can be found in the Kirk-Othmer Encyclopedia of Chemical Technology, 3rd edition, Vol.
7, pp. 168-182. This is because most compositions contain (a) a primary surfactant that is either a petroleum sulfonate or a synthetic hydrocarbyl sulfonate, and (b) a simple alcohol.

and co-surfactants including ethoxylated alcohols and sulfated ethoxylated alcohols.

Additionally, it is disclosed that alkyl and alkylaryl polyalkoxyalkylene sulfonates may also be used as cosurfactants. These compounds are generally manufactured by a three step process. In the first step of a typical process, an alcohol or alkylphenol is condensed with an alkylene oxide in the presence of sodium or potassium hydroxide to form an alkoxylate. This is then halogenated, generally by treatment with thionyl chloride or sulfuryl in the absence of a catalyst. lastly,
The halides are again generally converted to the sulfonates by reaction with sodium sulfide in the absence of catalysts.

The alkaline catalyst must be removed after the alkoxylation reaction since its presence inhibits the stability of the product.

[Problem that the invention seeks to solve]

The present invention aims to provide a process for producing alkoxy halides from alcohols or phenols using a single soluble inorganic catalyst.

[Means for solving problems]

According to the invention, an alcohol, a phenol of the formula R'-OH or an alcohol of the formula: an alkyl group having 24, preferably 8 to 20 carbon atoms and R and R4 are hydrogen atoms, or R and R3 are both alkyl groups having 1 to 12 carbon atoms and R4 is hydrogen thick, or R, R and R4 are each an alkyl group, and the total number of carbon atoms in these alkyl groups is in the range of 3 to 24. alkylalkoxy, arylalkoxy or alkylarylalkoxy having 1 to 15, preferably 4 to 10 alkoxy units per molecule by reacting with ethylene oxide and/or propylene oxide in the presence of a soluble metal or metal compound of the group Alkylalkoxy, consisting of producing an alcohol and reacting the reaction product directly with a halogenating agent in the continuous presence of a catalyst.

A method of making an arylalkoxy or alkylaryl alkoxy halide is provided.

Suitable catalysts include chlorides, hydroxides, alkoxides and alkanoates of lithium, magnesium, calcium, strontium and barium.

Other suitable catalysts include the above-mentioned compounds of sodium, potassium, rubidium and cesium solubilized with solubilizing agents. Suitable solubilizers include, for example, dipolar aprotic solvents such as dimethyl sulfoxide, crown ethers and polyalkoxy compounds having three or more alkoxy groups per molecule, such as dimethylpolyethylene glycol.

Catalyst promoters can also be used if desired. Known promoters for alkoxylation catalysts include phenols, carboxylic acids, polyols, aldehydes, ketones, amines, amides and inorganic acids.

Alkoxy distribution can be determined by catalyst selection.

If a broad distribution is desired, the catalyst is preferably a lithium compound.

On the other hand, if a narrow distribution is preferred, the catalyst is preferably a Group 11A metal compound in combination with a promoter.

Suitable halogenating agents are chlorinating agents such as thionyl chloride and sulfuryl chloride.

Pressures ranging from atmospheric pressure to 7 bar can be used for the alkoxylation step.

Pressure is not a critical parameter for the halogenation step, so it is particularly convenient to carry out the reaction at atmospheric pressure.

Alkoxylation is carried out at 100-260°C, preferably at 120°C.
It is suitable to carry out at a temperature in the range of ~190°C, and the halogenation is carried out at a temperature of 30-120°C, preferably 75-85°C.
It is suitable to carry out at a temperature in the range of °C.

The molar ratio of alkoxy alcohol to halogenating agent in the halogenation step is from 1:1 to 1:5, preferably from 1:1 to
A range of 1:1.5 is suitable.

The amount of catalyst used is preferably alcohol.

It ranges from 0.1 to 10% by weight, preferably from 0.2 to 1% by weight, expressed as phenol or alkylphenol weight %.

The reaction can be carried out in the presence or preferably in the absence of a solvent. Suitable solvents include 1,2-dichloroethane, toluene and chloroform.

〔Effect of the invention〕

The process according to the invention has the following advantages: (1) a single catalyst can be used for both the alkoxylation and halogenation reactions, thus saving the cost of using separate catalysts for each reaction; (2) Product neutralization and/or catalyst removal from the alkoxylation step is no longer necessary.

(3) Hydrated salts or bases do not require special drying (generally water is removed after catalyst addition in the alkoxylation reaction and before introducing the alkylene oxide).

(4) If the salt or base is added to the halogenation mixture at this stage, it will dissolve slowly and therefore will not adversely affect the halogenation reaction.

However, if a catalyst is used beforehand in the alkoxylation step, it is already solubilized.

(5) Inexpensive compounds such as hydroxides or alkoxides can be used as catalysts.

(6) The catalyst can be easily recovered by filtration or extraction with water.

As a result of the shortening of the reaction time in the halogenation step, polyalkylene chains are cleaved, e.g., polyoxydiethylene chains as described by O. Vinson et al. in Journal Society Cosmetic Chemistry, Vol. 31, pp. 329-337. The tendency to liberate 1,4-dioxane is reduced when . Therefore, both the yield and selectivity exhibited by the matching of the alkoxy distribution in the alcohol and the halide are improved, and product contamination by undesirable by-products is reduced.

〔Example〕

Hereinafter, the present invention will be explained with reference to Examples, in which Example 2 is not based on the present invention but is shown for comparison.

Example 1 Hexadecanol was mixed with strontium hydroxide (1% W/W)
) and phenol (1,5% W/W) at 100° C. under reduced pressure for 1 hour to remove water to a level of 0.07% W/W.

This was then reacted with ethylene oxide for 5 hours at 125° C. under a pressure of 4 bar, introducing 4 mol of ethylene oxide per mol of alcohol.

Unpurified ethoxy alcohol 016H33 (OCH2CH2) 40H (54.8g
.

0,1318) was heated with thionyl chloride (16,Bq, 0.1418) at 80°C with stirring.

013 NMR (nuclear magnetic resonance) spectrophotometry showed 90% conversion to ethoxy chloride after 2 hours, and GLG
(gas-liquid chromatography) is ethoxy alcohol 1
It was shown that 0.02 moles of 1,4-dioxane were produced per mole.

Hexdecanol was treated with potassium hydroxide (0.3% w/w) at 100° C. under reduced pressure to remove water. This was then reacted with ethylene oxide for 5 hours at 125° C. under a pressure of 4 bar, introducing 4 mol of ethylene oxide per mol of alcohol.

Unpurified ethoxy alcohol C16H33(OCH2C)12)40H(50,O
a.

0,1201 was heated with thionyl chloride (15,4Q, 0.129) 1) at 80°C with stirring.
.

013N MR spectrophotometry showed 26% conversion to ethoxy chloride after 2 hours and GLC showed 0.2 moles of 1,4-dioxane formed per mole of ethoxy alcohol.

As can be seen by comparing Examples 1 and 2, the effective ethoxylation-chlorination catalyst (strontium ion) in Example 1 is the less effective ethoxylation-chlorination catalyst in Example 2, where the ethoxylation catalyst is an ineffective chlorination catalyst.
gave a chlorination rate 3.5 times greater than that of

1,4-Dioxane production was 10 times greater in non-catalytic chlorination than in catalytic chlorination.

If the potassium compound is removed after ethoxylation, Example 2
A similarly low chlorination rate would be expected.

Generally, this is done in daily operation.

The above examples demonstrate the value of leaving a suitable ethoxylation catalyst in the ethoxy alcohol to catalyze the chlorination step.

Patent applicant The British Vitrolium Compagnie P, L, C.

Claims (10)

[Claims] (1) Alcohol, phenol or formula of formula R^1-OH: ▲ Numerical formula, chemical formula, table, etc.▼ [In the formula, R^1 is an alkyl group having 1 to 24 carbon atoms, R^ 2 is an alkyl group having 1 to 24 carbon atoms and R^3 and R^4 are hydrogen atoms, or R^2 and R^3 are both alkyl groups having 1 to 12 carbon atoms group, and R^4 is a hydrogen atom, or R^2, R^3, and R^4 are each an alkyl group, and the total number of carbon atoms in these alkyl groups is in the range of 3 to 24. ] When reacting an alkylphenol with ethylene oxide and/or propylene oxide to produce an alkylalkoxy, arylalkoxy or alkylarylalkoxy alcohol having 1 to 15 alkoxy units per molecule, the reaction is catalyzed according to the periodic table. No.
I Alkylalkoxy, arylalkoxy or alkylaryl, characterized in that it is carried out in the presence of a soluble metal or metal compound of Group A or Group IIA, and that the reaction product is reacted directly with a halogenating agent in the continuous presence of a catalyst. A method for producing an alkoxy halide. (2) R^1 is an alkyl group having 8 to 20 carbon atoms, or R^2 is an alkyl group having 8 to 20 carbon atoms, and R^3 and R^4 are hydrogen atoms; The method according to claim 1, wherein the alkoxy moiety further has 4 to 10 alkoxy units per molecule. (3) The method according to claim 1 or 2, wherein the catalyst is selected from the group consisting of chlorides, hydroxides, alkoxides and alkanoates of lithium, magnesium, calcium, strontium and barium. (4) Claim 1 or 2, wherein the catalyst is selected from the group consisting of chlorides, hydroxides, alkoxides and alkanoates of sodium, potassium, rubidium and cesium solubilized with a solubilizer. the method of. (5) The method according to claim 4, wherein the solubilizing agent is selected from the group consisting of dipolar aprotic solvents, crown ethers, and polyalkoxy compounds having three or more alkoxy groups per molecule. (6) The method according to any one of claims 1 to 5, wherein the alkoxylation reaction is carried out at a temperature in the range of 100 to 260°C. (7) A method according to any one of claims 1 to 6, wherein the alkoxylation reaction is carried out at a pressure in the range of atmospheric pressure to 7 bar. (8) The method according to any one of claims 1 to 7, wherein the halogenation reaction is carried out at a temperature in the range of 30 to 120°C. (9) The method according to any one of claims 1 to 8, wherein the molar ratio of alkoxy alcohol to halogenating agent is in the range of 1:1 to 1:5. (10) The method according to any one of claims 1 to 9, wherein the halogenating agent is thionyl chloride or sulfuryl chloride.